CN109666504A - A method of enhancing gas solubility behavior in viscous crude - Google Patents
A method of enhancing gas solubility behavior in viscous crude Download PDFInfo
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- CN109666504A CN109666504A CN201910074106.9A CN201910074106A CN109666504A CN 109666504 A CN109666504 A CN 109666504A CN 201910074106 A CN201910074106 A CN 201910074106A CN 109666504 A CN109666504 A CN 109666504A
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- viscous crude
- water
- solubility behavior
- gas solubility
- distillate
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
- B01F23/2319—Methods of introducing gases into liquid media
Abstract
The present invention provides a kind of method for enhancing gas solubility behavior in viscous crude, and the invention belongs to gas dissolutions and viscous crude to drop glutinous modification technology field.Appropriate fractions and/or water by being incorporated into viscous crude by the present invention, solubility of the CO in viscous crude system is improved while guaranteeing oil product stability, this fraction, which may be derived from viscous crude, may be derived from producing the own water in oil emulsion through own fraction, the water of distilling apparatus or thermal upgrading device, the present invention passes through the solubility behavior for strengthening CO in upgrading processes using the retrievable factor of extraction viscous crude itself, have many advantages, such as that incorporation component cheap and easy to get, simplification water-oil separating, process are convenient, therefore the value with good practical application.
Description
Technical field
The invention belongs to gas dissolutions and viscous crude to drop glutinous modification technology field, in particular to a kind of enhancing gas is in viscous crude
The method of solubility behavior.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
With the continuous aggravation of crude oil heaviness, in poor quality degree in world wide, the development and utilization of viscous crude are by extensive
Concern.However, Viscosity of Heavy Crude Oil is high, mobility is very poor, it is therefore necessary to which drop glutinous modification to viscous crude just can be carried out that pipe is defeated or shipping.
Thermal upgrading realizes that drop is glutinous based on the thermal cracking of heavy oil macromolecular, however the strong polycondensation tendency for being pyrolyzed free radical easily leads to system
Green coke is the critical bottleneck for restricting modification efficiency.Active hydrogen has effects that free radical is quenched, to delaying system green coke, enhancing
Modification effect is of great significance.Research points out, the newborn hydrogen activity that water gas shift reaction generates is strong, relative hydrogen cost
It is cheap, it is expected to as important substitution hydrogen source.Patent ZL107129827 is reported using Water gas shift/WGS new life hydrogen as active hydrogen
Realize the means of the glutinous modification of viscous crude drop in source.
It should be noted, however, that carrying out in water-gas upgrading processes in viscous crude, CO is to modify to the dissolution of viscous crude system
Primary premise, how however mass transfer serious limitation by its height glutinous characteristic of the gas to viscous crude system to enhance gas thick
Dissolution in oil is of great significance to optimizing process, exploitation efficient thick-oil modifying process.Cai etc. [Fuel, 2001,80
(8): 1065-1077. a kind of method for strengthening hydrogen mass transfer in petroleum component using solid additive] is reported.Abedi exists
Disclosed research report [Office of Scientific&Technical Information Technical Reports,
2002.] also indicate that such micro additive can significantly increase the dissolubility of hydrogen in a liquid in.Such additives are mainly
The porous adsorbing materials such as clay, catalyst fines, carbon black, aluminium oxide.But inventors have found that the reinforcing of this method is only table
See gas holdup and not actual solubility.Viscosity of Heavy Crude Oil is high, armaticity is strong, and the actual solubility for enhancing CO gas in viscous crude is to mention
Rise one of an important factor for viscous crude carries out water-gas modification effect.
Summary of the invention
Aiming at the shortcomings in the prior art, the present invention provides a kind of method for enhancing gas solubility behavior in viscous crude, this
Invention improves CO in viscous crude system by the way that appropriate fractions and/or water are incorporated into viscous crude while guaranteeing oil product stability
In solubility, this fraction may be derived from viscous crude and may be derived from producing oily cream through own fraction, the water of distilling apparatus or thermal upgrading device
Own water in shape liquid, the present invention pass through the dissolution row for strengthening CO in upgrading processes using the retrievable factor of extraction viscous crude itself
For, have many advantages, such as to mix that component is cheap and easy to get, it is convenient to simplify water-oil separating, process, therefore have good practical application it
Value.
One of the objects of the present invention is to provide a kind of methods for enhancing gas solubility behavior in viscous crude.
The second object of the present invention is to provide the application of the above method.
To achieve the above object, the present invention relates to following technical schemes:
The first aspect of the invention provides a kind of method for enhancing gas solubility behavior in viscous crude, the method packet
It includes: mixing distillate into viscous crude and/or water obtains stablizing mixing viscous crude system；Mixing viscous crude system will be stablized in CO atmosphere
It is stirred mass transfer.
A method of enhancing gas solubility behavior in viscous crude, specific steps are as follows:
S1, viscous crude raw material is weighed, mixes distillate and/or water thereto, heat temperature raising carries out high-speed stirred and stablized
Mix viscous crude system；
S2, stable mixing viscous crude system is heated in CO atmosphere mass transfer temperature, be stirred to pressure no longer
When variation, stop stirring and standing.
Further, the gas is CO gas；
Further, in the step S1,
For the boiling range of the distillate within the scope of 320-480 DEG C, the distillate of the boiling range section can be thick with high armaticity
Oil has good complex colloid stability, and boiling range is too low can not be preferably compatible with viscous crude, and boiling range is excessively high can not effectively to enhance CO
Dissolution, mixed ratio are the 2-20% of viscous crude material quality, and the mixed ratio of the water is the 5-20% of viscous crude raw material volume, are mixed
Enter the too low purpose for being unable to reach effectively enhancing gas dissolution of ratio, the economy of the excessively high influence means of mixed ratio；
Further, the distillate is own fraction of the viscous crude through distilling apparatus or thermal upgrading device；
The water is the own water being directly derived from extraction oil emulsion；
Further, in the step S1, mixing time 0.5-2.5h, revolving speed 2000-8000rpm；Pass through control
Revolving speed and mixing time, advantageously ensure that system is sufficiently mixed uniformity；
For viscous crude-distillate mixed system, whipping temp is 100-130 DEG C；
For viscous crude-water mixed system, whipping temp is 70-90 DEG C；
To guarantee mixed system uniformity, for viscous crude-distillate-water mixed system, preferably viscous crude and distillate
It is first stirred, obtains miscella, control mixing time is 0.5-2.5h, revolving speed 2000-8000rpm, whipping temp 100-
130℃；Then miscella and water are stirred, control mixing time is 0.5-2.5h, revolving speed 2000-8000rpm, stirring
Temperature is 70-90 DEG C.
Further, in the step S2,
CO pressure is 2-12MPa, and mass transfer temperature is 200-350 DEG C；Revolving speed is 200-500rpm；Time of repose is 1-3h.
By control above-mentioned condition and parameter, stablize in mixing viscous crude system so that CO is more sufficiently and quickly dissolved in.
The second aspect of the invention provides the above method in viscous crude and drops the application in glutinous modification.
Advantageous effects of the invention: the retrievable factor of technical solution of the present invention effective use extraction viscous crude itself increases
Strong solubility behavior of the CO in viscous crude is put forward for the first time molten in viscous crude by the way that the own fraction of viscous crude and own water enhancing CO is added
Solution behavior, therefore be of great significance for promoting viscous crude progress water-gas modification effect.The method has incorporation component honest and clean
Valence is easy to get, simplifies water-oil separating, the advantage that process is convenient；Therefore with the value of good practical application.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As previously mentioned, viscous crude carry out water-gas upgrading processes in, CO to the dissolution of viscous crude system be modification it is primary before
It mentions, however mass transfer serious limitation by its height glutinous characteristic of the gas to viscous crude system, it is molten in viscous crude how to enhance gas
Solution is of great significance to optimizing process, exploitation efficient thick-oil modifying process.
In view of this, providing a kind of enhancing gas solubility behavior in viscous crude in the specific embodiment of the present invention
Method, which comprises mix distillate and/or water into viscous crude and obtain stablizing mixing viscous crude system；It is mixed stablizing
Viscous crude system is stirred mass transfer in CO atmosphere.
In still another embodiment of the invention, a kind of method for enhancing gas solubility behavior in viscous crude, tool are provided
Body step are as follows:
(1) a certain amount of viscous crude raw material, incorporation certain proportion appropriate fractions oil or/and water are weighed, at a certain temperature high speed
Stir certain time；
(2) will blending treated that viscous crude is placed in autoclave, continuously purged in net autoclave side by side using CO gas
Air begins heat to mass transfer temperature；
(3) it is filled with certain pressure CO gas into autoclave, starts to be stirred into the mass transfer stage, when pressure no longer becomes in kettle
When change, stop stirring and standing a period of time.
In still another embodiment of the invention, the gas is CO gas；
In still another embodiment of the invention, in the step (1),
For the boiling range of the distillate within the scope of 320-480 DEG C, mixed ratio is the 2-20% of viscous crude material quality, described
The mixed ratio of water is the 5-20% of viscous crude raw material volume；
In still another embodiment of the invention, the distillate is the viscous crude through distilling apparatus or thermal upgrading device
Own fraction；
The water is the own water being directly derived from extraction oil emulsion；
In still another embodiment of the invention, in the step (1), mixing time 0.5-2.5h, revolving speed is
2000-8000rpm；
For viscous crude-distillate mixed system, whipping temp is 100-130 DEG C；
For viscous crude-water mixed system, whipping temp is 70-90 DEG C；
To guarantee mixed system uniformity, for viscous crude-distillate-water mixed system, preferably viscous crude and distillate
It is first stirred, obtains miscella, control mixing time is 0.5-2.5h, revolving speed 2000-8000rpm, whipping temp 100-
130℃；Then miscella and water are stirred, control mixing time is 0.5-2.5h, revolving speed 2000-8000rpm, stirring
Temperature is 70-90 DEG C.
In still another embodiment of the invention, in the step (2), mass transfer temperature is 200-350 DEG C；
In still another embodiment of the invention, in the step (3), CO pressure is 2-12MPa；Revolving speed is 200-
500rpm；Time of repose is 1-3h.
In still another embodiment of the invention, the above method is provided in viscous crude and drops the application in glutinous modification.
It in order to which the present invention is furture elucidated, is elaborated below with specific embodiment to the present invention, these embodiments are complete
Be entirely it is illustrative, they be only used to the present invention specifically describe, be not construed as limitation of the present invention.
Embodiment 1
By 60g viscous crude A, (120 DEG C of viscositys are 5322mm2/ s) and viscous crude material quality score 8wt% distillate A (boiling range
350-420 DEG C) 1h is stirred under 120 DEG C, 4000rpm revolving speed after be added in 300mL autoclave, utilize the continuous row of purging of CO
200 DEG C are begun heat to after net air, be subsequently charged with the CO of about 2.0MPa and starts to stir, and mixing speed 300rpm works as pressure
Stop stirring when power no longer changes, stand 1.5h, is sampled at this time using in gas solubility measuring system measurement sample
CO meltage.The results show that solubility of the CO in viscous crude is 0.0768mol/kg under 200 DEG C of temperature, pressure 2.012MPa.
Embodiment 2
By 60g viscous crude A, (120 DEG C of viscositys are 5322mm2/ s) and viscous crude material quality score 8wt% distillate A (boiling range
350-420 DEG C) 1h is stirred under 120 DEG C, 4000rpm revolving speed after be added in 300mL autoclave, utilize the continuous row of purging of CO
250 DEG C are begun heat to after net air, be subsequently charged with the CO of about 6.0MPa and starts to stir, and mixing speed 300rpm works as pressure
Stop stirring when power no longer changes, stand 1.5h, is sampled at this time using in gas solubility measuring system measurement sample
CO meltage.The results show that solubility of the CO in viscous crude is 0.2540mol/kg under 250 DEG C of temperature, pressure 6.012MPa.
Embodiment 3
By 60g viscous crude B, (100 DEG C of viscositys are 2995mm2/ s) and volume fraction be raw material 5% water in 80 DEG C, 3000rpm
It is added in 300mL autoclave after stirring 1h under revolving speed, is continuously purged using CO and begin heat to 200 DEG C after emptying air,
It is subsequently charged with the CO of about 4.0MPa and starts to stir, mixing speed 300rpm stops stirring when pressure no longer changes, and stands
1.5h is sampled utilizes the CO meltage in gas solubility measuring system measurement sample at this time.The results show that temperature 200
DEG C, solubility of the CO in viscous crude is 0.1675mol/kg under pressure 4.012MPa.
Embodiment 4
By 60g viscous crude A, (120 DEG C of viscositys are 5322mm2/ s) and viscous crude material quality score 8wt% distillate A (boiling range
350-420 DEG C) stirring 1h obtains mixed raw material under 120 DEG C, 4000rpm revolving speed, the water of volume fraction 5% is added thereto,
It is added after stirring 1h under 80 DEG C, 4000rpm revolving speed into 300mL autoclave, is continuously purged using CO after emptying air
200 DEG C are begun heat to, the CO of about 2.0MPa is subsequently charged with and starts to stir, stops stirring when pressure no longer changes, is stood
1.5h is sampled utilizes the CO meltage in gas solubility measuring system measurement sample at this time.The results show that temperature 200
DEG C, solubility of the CO in viscous crude is 0.1042mol/kg under pressure 2.113MPa.
Experimental example 1
By 60g viscous crude A, (120 DEG C of viscositys are 5322mm2/ s) it is added after stirring 1h under 120 DEG C, 4000rpm revolving speed
In 300mL autoclave, is continuously purged using CO and begin heat to 200 DEG C after emptying air, be subsequently charged with about 2.0MPa's
CO simultaneously starts to stir, mixing speed 300rpm, stops stirring when pressure no longer changes, and stands 1.5h, is sampled at this time
Utilize the CO meltage in gas solubility measuring system measurement sample.The results show that under 200 DEG C of temperature, pressure 2.157MPa
Solubility of the CO in viscous crude is 0.0583mol/kg.
Experimental example 2
By 60g viscous crude A, (120 DEG C of viscositys are 5322mm2/ s) it is added after stirring 1h under 120 DEG C, 4000rpm revolving speed
In 300mL autoclave, is continuously purged using CO and begin heat to 250 DEG C after emptying air, be subsequently charged with about 6.0MPa's
CO simultaneously starts to stir, mixing speed 300rpm, stops stirring when pressure no longer changes, and stands 1.5h, is sampled at this time
Utilize the CO meltage in gas solubility measuring system measurement sample.The results show that under 250 DEG C of temperature, pressure 6.015MPa
Solubility of the CO in viscous crude is 0.2068mol/kg.
Experimental example 3
By 60g viscous crude B, (100 DEG C of viscositys are 2995mm2/ s) it is added in 300mL autoclave, it is continuously purged using CO
200 DEG C are begun heat to after emptying air, the CO of about 4.0MPa is subsequently charged with and starts to stir, mixing speed 300rpm, when
Stop stirring when pressure no longer changes, stand 1.5h, is sampled at this time using in gas solubility measuring system measurement sample
CO meltage.The results show that solubility of the CO in viscous crude is 0.1352mol/kg under 200 DEG C of temperature, pressure 4.204MPa.
It can see by the result of embodiment and experimental example, utilize incorporation appropriate fractions oil provided by the invention or water
Method can significantly improve equilbrium solubility of the CO in viscous crude, enhance its solubility behavior, appropriate fractions oil and coexisting for water can
Further strengthen the dissolution of CO gas, this fraction may be derived from viscous crude can through own fraction, the water of distilling apparatus or thermal upgrading device
The own water being derived from extraction oil emulsion, therefore the present invention strengthens the retrievable factor of effective use extraction viscous crude itself
The solubility behavior of CO in upgrading processes is of great significance to promote the glutinous modification efficiency of viscous crude drop, has incorporation component cheap
It is easy to get, simplifies water-oil separating, the advantages that process is convenient.
It should be noted that above example is only used to illustrate the technical scheme of the present invention rather than is limited.Although ginseng
It is described the invention in detail according to given example, but those skilled in the art can be as needed to this hair
Bright technical solution is modified or replaced equivalently, without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. a kind of method for enhancing gas solubility behavior in viscous crude, which is characterized in that the described method includes: being mixed into viscous crude
Distillate and/or water obtain stablizing mixing viscous crude system；Mixing viscous crude system will be stablized and be stirred mass transfer in CO atmosphere.
2. a kind of method for enhancing gas solubility behavior in viscous crude as described in claim 1, which is characterized in that specific steps
Are as follows:
S1, viscous crude raw material is weighed, mixes distillate and/or water thereto, heat temperature raising carries out high-speed stirred and obtains stablizing mixing
Viscous crude system；
S2, stable mixing viscous crude system is heated in CO atmosphere mass transfer temperature, is stirred to pressure and no longer changes
When, stop stirring and standing.
3. a kind of method for enhancing gas solubility behavior in viscous crude as described in claim 1, which is characterized in that the gas
For CO gas.
4. a kind of method for enhancing gas solubility behavior in viscous crude as described in claim 1, which is characterized in that the step
In S1, for the boiling range of the distillate within the scope of 320-480 DEG C, mixed ratio is the 2-20% of viscous crude material quality, the water
Mixed ratio be viscous crude raw material volume 5-20%.
5. a kind of method for enhancing gas solubility behavior in viscous crude as described in claim 1, which is characterized in that the fraction
Oil is own fraction of the viscous crude through distilling apparatus or thermal upgrading device；
The water is the own water being directly derived from extraction oil emulsion.
6. a kind of method for enhancing gas solubility behavior in viscous crude as described in claim 1, which is characterized in that the step
In S1, mixing time 0.5-2.5h, revolving speed 2000-8000rpm.
7. a kind of method for enhancing gas solubility behavior in viscous crude as described in claim 1, which is characterized in that for thick
Oil-distillate mixed system, whipping temp are 100-130 DEG C；
For viscous crude-water mixed system, whipping temp is 70-90 DEG C.
8. a kind of method for enhancing gas solubility behavior in viscous crude as described in claim 1, which is characterized in that for thick
Oil-distillate-water mixed system, preferably viscous crude and distillate are first stirred, and obtain miscella, and control mixing time is 0.5-
2.5h, revolving speed 2000-8000rpm, whipping temp are 100-130 DEG C；Then miscella and water are stirred, control stirring
Time is 0.5-2.5h, and revolving speed 2000-8000rpm, whipping temp is 70-90 DEG C.
9. a kind of method for enhancing gas solubility behavior in viscous crude as described in claim 1, which is characterized in that the step
In S2,
CO pressure is 2-12MPa, and mass transfer temperature is 200-350 DEG C；Revolving speed is 200-500rpm；Time of repose is 1-3h.
10. any one of claim 1-9 the method drops the application in glutinous modification in viscous crude.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760583A (en) * | 2005-11-10 | 2006-04-19 | 中国石油大学(北京) | Method for implementing storage and/or transportation of solid state mixed in oil-gas |
| CN1814714A (en) * | 2005-02-03 | 2006-08-09 | 石油大学(北京) | Method for generating aqua compound |
| CN101649734A (en) * | 2009-09-09 | 2010-02-17 | 西南石油大学 | Method for integrally catalyzing, reforming, reducing viscosity, extracting and transporting thick oil |
| CN107129827A (en) * | 2017-07-06 | 2017-09-05 | 中国石油大学(华东) | A kind of glutinous modification intensifying method of thick oil hydrothermal drop |
-
2019
- 2019-01-25 CN CN201910074106.9A patent/CN109666504A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1814714A (en) * | 2005-02-03 | 2006-08-09 | 石油大学(北京) | Method for generating aqua compound |
| CN1760583A (en) * | 2005-11-10 | 2006-04-19 | 中国石油大学(北京) | Method for implementing storage and/or transportation of solid state mixed in oil-gas |
| CN101649734A (en) * | 2009-09-09 | 2010-02-17 | 西南石油大学 | Method for integrally catalyzing, reforming, reducing viscosity, extracting and transporting thick oil |
| CN107129827A (en) * | 2017-07-06 | 2017-09-05 | 中国石油大学(华东) | A kind of glutinous modification intensifying method of thick oil hydrothermal drop |
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Application publication date: 20190423 |